KR101410337B1 - Curable silicone composition and electronic component - Google Patents

Abstract

A curable silicone composition comprising at least the following components: (A) an epoxy-containing organopolysiloxane; (B) a curing agent for epoxy resin; and (C) an epoxy compound represented by the specific general formula; is characterized by excellent handleability and reduced oil-bleeding, and, when cured, forms a cured body of excellent flexibility and adhesion.

Description

[0001] Curable silicone composition and electronic component [0002]

The present invention relates to a curable silicone composition and electronic components. More particularly, the present invention relates to a curable silicone composition which is characterized by excellent handling workability and reduced oil-bleeding and which forms a cured product with good flexibility and adhesion upon curing. The present invention also relates to an electronic component which is sealed or bonded by a cured product of the above-mentioned composition and which is characterized by excellent reliability.

BACKGROUND ART Conventionally, a curable resin composition used for a sealing agent and an adhesive for electric and electronic parts, for example, a cured product obtained by curing a curable epoxy resin composition or the like is characterized by a high elastic modulus and accordingly a high rigidity. Thus, the use of such a cured product with electrical or electronic components is associated with problems such as, for example, the occurrence of high stresses occurring under thermal expansion conditions. Another problem associated with the use of cured products of the above-mentioned compositions is the buckling of electrical or electronic components or substrates and the formation of cracks at the interface between the resin cured product or the cured resin and the electrical or electronic component, Which in some cases can lead to the destruction of each part.

It has been proposed to prepare a curable silicone composition from a curing agent for an epoxy-containing organopolysiloxane and an organopolysiloxane resin in order to reduce the stress that may occur in the above-mentioned cured product (Japanese Unexamined Patent Application, Quot; Open Publication ") 2005-154766, 2006-306953, and 2006-306954). However, when such a curable silicone composition is used in an adhesive of an electric or electronic component, an oil-bleeding problem of some component of the composition on the external surface of the cured product occurs, which causes contamination of the component.

It is an object of the present invention to provide a curable silicone composition characterized by the ability to form a cured article characterized by good handling performance and reduced oil-bleeding and excellent flexibility and adhesion. Another object is to provide an electronic component having high reliability.

DESCRIPTION OF THE INVENTION

More particularly, the present invention provides a curable silicone composition comprising at least the following components:

(A) an organopolysiloxane (A ₁ ) represented by the average unit formula of the formula ( ₁ ) and / or a diorganopolysiloxane (A ₂ ) represented by the formula (2) containing two or more epoxy-

(B) a curing agent for an epoxy resin and

(C) an epoxy compound of the formula (4).

^{_{(R 1 3 SiO 1/2}} ) a (R 2 2 SiO 2/2) b (R 3 SiO 3/2) c

In the above formula (1)

R ¹ , R ² and R ³ may be the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group or an epoxy-containing monovalent hydrocarbon group, but at least 20 mole% of the group represented by R ³ is an aryl group ,

a, b, and c satisfy the conditions of 0? a? 0.8, 0? b? 0.8, 0.2? c? 0.9, and a + b + c =

AR ⁵ - (R ⁴ ₂ SiO) _m R ⁴ ₂ Si-R ⁵ -A

In the above formula (2)

R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having no unsaturated aliphatic bond,

R < ⁵ > is a divalent organic group,

A is a siloxane residue radical represented by the average unit formula of the formula (3)

m is an integer of 1 or more.

(XR ⁴ ₂ SiO _1/2 ) _d (SiO _4/2 ) _e

In the above formula (3)

R ⁴ is the same as defined above,

X is a single bond, a hydrogen atom, a group represented by R ⁴ , an epoxy-containing monovalent organic group or an alkoxysilylalkyl group, but one or more groups represented by X in one molecule are single bonds and two The above group is an epoxy-containing monovalent organic group,

d is a positive number,

e is a positive number,

d / e is a number in the range of 0.2 to 4.

In the above formula (4)

R ⁸ is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms,

f is an integer of 0 to 4;

Further, the electronic component according to the present invention is sealed or bonded using the above-mentioned curable silicone composition.

Effects of the Invention

The curable silicone composition of the present invention is characterized by excellent handling workability and is effective because the contamination of the surface of the cured product due to reduced oil-bleeding is small. Further, the cured product of the composition can be adhered to various substrates, has excellent flexibility and adhesion, and generates a reduced internal stress under the effect of thermal expansion. In addition, these components are characterized by excellent reliability because electronic components manufactured in accordance with the present invention are sealed or adhered using the cured silicone composition compositions described above.

1 is a cross-sectional view of an LSI as an example of an electronic component of the present invention.

Reference number:

1 semiconductor element

2 substrate

3 Ball grid

4 Heat spreader

5 Adhesive

6 Heat insulating material

7 Heat sink

8 Heat insulating material

First, the curable silicone composition of the present invention will be described in more detail.

Component (A) of the composition is the main component of the composition. The component is an organopolysiloxane (A ₁ ) represented by the average unit formula of the formula ( ₁ ) and / or a diorganosiloxane (A ₂ ) of the formula ( ₂ ).

Formula 1

^{_{(R 1 3 SiO 1/2}} ) a (R 2 2 SiO 2/2) b (R 3 SiO 3/2) c

(2)

AR ⁵ - (R ⁴ ₂ SiO) _m R ⁴ ₂ Si-R ⁵ -A

In component (A ₁ ), R ¹ , R ² and R ³ are the same or different and are composed of a substituted or unsubstituted monovalent hydrocarbon group or an epoxy-containing monovalent organic group. The above-mentioned monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl or similar alkyl groups; Cyclopentyl, cyclohexyl, cycloheptyl or similar cycloalkyl groups; Vinyl, allyl, butenyl, pentenyl, hexenyl or similar alkenyl groups; Phenyl, tolyl, xylyl or similar aryl groups; Benzyl, phenethyl, phenylpropyl or similar aralkyl groups; And chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or similar halogenated alkyl groups. Most preferred are alkyl and aryl groups, especially methyl and phenyl groups. The epoxy-containing monovalent organic groups include 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl or similar glycidoxyalkyl groups; (3,4-epoxycyclohexyl) ethyl, 3- (3,4-epoxycyclohexyl) propyl, 2- Alkylalkyl groups; And 4-oxiranylbutyl, 8-oxiranyloctyl, or similar oxiranylalkyl groups. Of these groups, glycidoxyalkyl and epoxycycloalkylalkyl groups are most preferred, especially 3-glycidoxypropyl and 2- (3,4-epoxycyclohexyl) ethyl groups. In the formula (1), two or more groups represented by R ¹ , R ² and R ³ are the above-mentioned epoxy-containing monovalent organic groups.

In the general formula (1), at least 20 mol%, preferably at least 50 mol%, and most preferably at least 80 mol% of the total group of R ³ is an aryl group. If the content of aryl groups for the entire group represented by R ³ in one molecule is lower than the recommended lower limit, this will reduce the adhesion of the cured product obtained from the composition or reduce the mechanical strength of the cured product. It is recommended that such aryl groups include phenyl groups.

In formula (1), a, b and c are numbers satisfying the conditions of 0? A? 0.8, 0? B? 0.8, 0.2? C? 0.9 and a + b + c = In Formula 1, a is a number that represents the ratio of siloxane units of the formula R ¹ ₃ SiO _1/2. When the component is composed solely of siloxane units of the formula R ³ SiO _3/2 , the components become excessively viscous, which reduces the handling workability of the resulting composition, so that a satisfies 0 <a ≦ 0.8, It is recommended that the condition of 0.3? A? 0.8 is satisfied. In formula (1), b is a number representing the ratio of siloxane units of the formula R ² ₂ SiO _2/2 . B should be a number satisfying the condition of 0? B? 0.6 in order that the component has an optimum molecular weight, prevents the component from bleeding from the obtained cured product, and provides a cured product excellent in mechanical strength . In the formula (1), c represents the ratio of siloxane units of the formula R ³ SiO _3/2 . C is a number satisfying the condition of 0.4 &amp;le; c &amp;le; 0.9 to provide a cured product which provides excellent handling workability of the composition and has excellent adhesion, excellent mechanical strength and flexibility.

The content of the epoxy-containing monovalent organic group in the component (A ₁ ) is not particularly limited, but the epoxy equivalent of the component (the mass average molecular weight of the component is divided by the number of epoxy groups in one molecule) ) Is in the range of 100 to 2,000, preferably 100 to 1,000, and most preferably 100 to 700. [ If the epoxy equivalent is below the recommended lower limit, the flexibility of the cured product obtained from the composition will be reduced. On the other hand, if the epoxy equivalent exceeds the recommended upper limit, the curing ability of the composition will be lowered and the adhesion and mechanical strength of the cured product obtained by curing the composition will be reduced. The component (A ₁ ) may also comprise a mixture of one type of organopolysiloxane or two or more types of organopolysiloxanes. The form of the component (A ₁ ) at 25 캜 is not particularly limited, and may be in liquid or solid form. When component (A ₁ ) is in the solid form, component (A ₁ ) may be dissolved or heated in an organic solvent to uniformly mix with other components. It is preferable to use the component in liquid form at 25 DEG C from the viewpoint of excellent pearl synthesis and handling workability. The mass average molecular weight of the component (A ₁ ) is not particularly limited, but it is recommended that the properties are in the range of 500 to 10,000, preferably 750 to 3,000.

The above-mentioned component (A ₁ ) can be exemplified by organopolysiloxanes of the following formulas, wherein a, b and c are as defined above, but a and b both can not be 0, and c ' And c "are numbers satisfying the condition of 0.1 <c '<0.8, 0 <c"<0.2, 0.2 (c' + c ") ≦ 0.9 and 0.2 ≦ c '/ (c' + c" , G is a 3-glycidoxypropyl group, and E is a 2- (3,4-epoxycyclohexyl) ethyl group.

The method for producing the component (A ₁ ) is not particularly limited. For example, the following methods are possible:

(1) an alkoxysilane having an epoxy-containing monovalent organic group, such as 3-glycidoxypropyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, A method of co-hydrolyzing and condensing silane;

(2) a process in which a silanol-containing organopolysiloxane obtained by hydrolysis and condensation of an alkoxysilane having an epoxy-containing monovalent organic group and phenyltrichlorosilane or phenyltrialkoxysilane is subjected to a dealcoholization reaction ;

(3) organopolysiloxanes having silicon-bonded hydrogen atoms prepared by cohydrolysis and condensation of phenyltrichlorosilane or phenyltrialkoxysilane in the presence of dimethylchlorosilane or in the presence of a similar silane with silicon-bonded hydrogen atoms And an olefin having an epoxy-containing monovalent organic group;

(4) organopolysiloxanes prepared by hydrolyzing and condensing phenyltrichlorosilane or phenyltrialkoxysilane, dimethylsiloxane having both molecular terminals capped with trimethylsiloxy groups and methyl {2- (3,4-epoxychloro Hexyl) ethyl} siloxane or a copolymer of dimethylsiloxane and methyl (3-glycidoxypropyl) siloxane in which both molecular terminals are capped with trimethylsiloxy groups in the presence of a basic catalyst;

(5) the formula C ₆ H ₅ SiO _3/2 siloxane unit of organopolysiloxane composed of a polysiloxane and a cyclic methyl {2- (3,4-epoxycyclohexyl) ethyl} siloxane or a cyclic methyl (3-glycidoxy Propyl) siloxane in the presence of a basic catalyst or

(6) an organopolysiloxane consisting of siloxane units of the formula C ₆ H ₅ SiO _3/2 and cyclic {2- (3,4-epoxycyclohexyl) ethyl} siloxane or cyclic methyl (3-glycidoxypropyl ) Siloxane and cyclic dimethylsiloxane in the presence of an acidic or basic catalyst.

In component (A ₂ ), R ⁴ may be a substituted or unsubstituted monovalent hydrocarbon group that does not have an aliphatic unsaturated group. Specific examples of the R ⁴ group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl or similar alkyl groups; Cyclopentyl, cyclohexyl, cycloheptyl or similar cycloalkyl groups; Phenyl, tolyl, xylyl or similar aryl groups; Benzyl, phenethyl, phenylpropyl or similar aralkyl groups; 3-chloropropyl, 3,3,3-trifluoropropyl or similar halogenated alkyl groups. Most preferred are alkyl groups, especially methyl groups. In Formula 2, R ⁵ is a divalent organic group such as ethylene, methylethylene, propylene, butylene, pentylene, hexylene or similar alkylene groups; Ethyleneoxyethylene, ethyleneoxypropylene, ethyleneoxybutylene, propyleneoxypropylene or similar alkyleneoxyalkylene groups. An alkylene group, particularly an ethylene group, is preferred. In the general formula (2), m is an integer of 1 or more and represents the degree of polymerization of the diorganopolysiloxane contained in the main chain of the molecule. In view of the improved flexibility of the cured product of the composition, m should be 10 or greater. The upper limit of the m value is not particularly limited, but is preferably a value such that m does not exceed 500.

In addition, in formula (2), A is a siloxane-residue radical represented by the average unit formula of formula (3).

(3)

(XR ⁴ ₂ SiO _1/2 ) _d (SiO _4/2 ) _e

In the above formula (3)

R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated group.

This group may be the same as that exemplified above, and among these, an alkyl group, particularly a methyl group, is preferable. In Formula (3), X is a single bond, a hydrogen atom, a group represented by R ⁴ , an epoxy-containing monovalent organic group, or an alkoxysilylalkyl group. The groups represented by R &lt; ⁴ &gt; can be exemplified in the same group as described above. The above epoxy-containing monovalent organic groups may be the same as those represented by R ¹ , R ² and R ³ . The alkoxysilylalkyl group may be exemplified by trimethoxysilylethyl, trimethoxysilylpropyl, dimethoxymethylsilylpropyl, methoxydimethylsilylpropyl, triethoxysilylethyl or tripropoxysilylpropyl groups. However, within one molecule, at least one X group is a single bond, and the bond is used to bond to the R ⁵ group in the diorganopolysiloxane mentioned above. In addition, at least one X group in one molecule must contain an epoxy-containing monovalent organic group, preferably a glycidoxyalkyl group, most preferably a 3-glycidoxypropyl group. In the formula (3), d is a positive number, e is a positive number, and d / e is a number of 0.2 to 4. [

The molecular weight of the component (A ₂ ) is not particularly limited, but it is recommended that the mass average molecular weight is in the range of 500 to 1,000,000. The form of the component (A ₂ ) at 25 캜 is not particularly limited, but a liquid form is preferred. The viscosity of the component (A ₂ ) at 25 占 폚 is 50 to 1,000,000 mPa 占 퐏. A method for producing the component (A ₂ ) is described, for example, in Japanese Patent Application Laid-Open No. H06-56999.

In the composition of the present invention, component (A) may comprise the above-mentioned component (A ₁ ) or component (A ₂ ) or a mixture thereof. Component (A) is component (A ₁₎ and the component case (A ₂₎ is a mixture of component (A ₂₎ a but the amount is not particularly limited, which can be used, component (A ₂₎ a component (A ₁₎ 100 parts by mass per Is preferably contained in an amount of 0.1 to 800 parts by mass, preferably 1 to 500 parts by mass, and most preferably 10 to 200 parts by mass. When the component (A ₂ ) is used in an amount lower than the recommended lower limit, the flexibility of the cured product due to curing of the composition will be lowered and, on the other hand, if the content of the component (A ₂ ) exceeds the recommended upper limit , The resulting composition will have an increased viscosity.

Component (B) which is a curing agent for an epoxy resin reacts with the epoxy group of the component (A) and is used as a preparation for curing the composition. The preparation is preferably a component containing at least two functional groups reactive with the epoxy group in one molecule. Examples of the above-mentioned functional groups include a primary amine group, a secondary amine group, a hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, an acid anhydride group, a mercapto group or a silanol group. In view of better reactivity and pot life, phenolic hydroxyl groups are preferred. In particular, component (B) is selected from the group consisting of phenolic hydroxyl groups, such as phenol novolak resins, cresol novolak resins, bisphenol A type compounds or similar phenolic resins; And a compound containing an organopolysiloxane having a phenolic hydroxyl group. It is preferable to use an organosiloxane containing two or more phenolic hydroxyl groups in one molecule. The equivalent of the phenolic hydroxyl group (this is the value obtained by dividing the mass average molecular weight of the component by the number of phenolic hydroxyl groups contained in one molecule) does not exceed 1,000, and 500 for better reactivity It is recommended not to exceed.

The organosiloxane of formula (5) is recommended because the provision of organosiloxanes having phenolic hydroxyl groups of component (B) improves the flexibility of the cured product obtained by curing the composition.

R ⁶ ₃ Si0 (R ⁶ ₂ SiO) _n SiR ⁶ ₃

In the above formula (5)

R ⁶ may be the same or different and is a monovalent organic group containing a substituted or unsubstituted monovalent hydrocarbon group or a phenolic hydroxyl group.

The above-mentioned monovalent hydrocarbon groups are as exemplified above, and among them, alkyl group and aryl group are preferable, and methyl group and phenyl group are particularly preferable. Organic groups containing a phenolic group can be exemplified by groups represented by the following formulas. In these following formulas, R ⁷ is a divalent organic group such as ethylene, methylethylene, propylene, butylene, pentylene, hexylene or similar alkylene groups; Ethyleneoxyethylene, ethyleneoxypropylene, ethyleneoxybutylene, propyleneoxypropylene or similar alkyleneoxyalkylene groups. An alkylene group, particularly a propylene group, is preferred.

In formula (5), n is an integer ranging from 0 to 1,000, preferably from 0 to 100, and most preferably from 0 to 20. If n exceeds the recommended upper limit, this will reduce the compatibility with component (A) and the industrial handling workability.

The above-mentioned component (B) is exemplified by the organosiloxanes of the formulas shown below, wherein x is an integer from 1 to 20 and y is an integer from 2 to 10.

The method which can be used for the production of the component (B) is not particularly limited. For example, component (B) can be obtained by hydrosilylation of an organopolysiloxane having a silicon-bonded hydrogen atom with an alkenyl-containing phenol compound.

The form of the component (B) at 25 DEG C is not particularly limited, and it may be in a liquid or solid form. A liquid form is preferable from the viewpoint of easier handling workability with other components. It is recommended that the viscosity of the liquid component (B) at 25 占 폚 is in the range of 1 to 1,000,000 mPa 占 퐏, preferably 10 to 5,000 mPa 占 퐏. If the viscosity at 25 占 폚 is lower than the recommended lower limit, the resulting cured product will have a reduced mechanical strength. On the other hand, if the viscosity exceeds the recommended upper limit, this will reduce the industrial handling workability of the composition.

The amount by which the component (B) can be used in the composition is not particularly limited, but it is recommended to use the component (B) in an amount of generally 0.1 to 500 parts by mass, preferably 0.1 to 200 parts by mass, per 100 parts by mass of the component (A) do. When component (B) contains a phenolic hydroxyl group, the molar ratio of the phenolic hydroxyl groups contained in component (B) to the total epoxy groups contained in the composition is from 0.2 to 5, preferably from 0.3 to 2.5 , And most preferably 0.8 to 1.5. If the molar ratio of the phenolic hydroxyl groups contained in component (B) to the total epoxy groups contained in the composition is lower than the recommended lower limit, it will be difficult to ensure complete curing of the resulting composition. On the other hand, if the above-mentioned ratio exceeds the recommended upper limit, it will degrade the mechanical properties of the cured product obtained from the composition.

Component (C), which is an epoxy compound, is used in the composition to improve adhesion and to limit oil-bleeding to the surface of the cured product. Component (C) is a compound of formula (4).

Formula 4

In the above formula (4)

R ⁸ is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms.

The above-mentioned monovalent hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl or similar alkyl groups; Cyclopentyl, cyclohexyl, cycloheptyl or similar cycloalkyl groups; Methoxyethyl, ethoxyethyl or similar ethoxy-substituted alkyl groups; Vinyl, allyl, butenyl or similar alkenyl groups; Cyclopentenyl, cyclohexenyl or similar cycloalkenyl group; Phenyl, tolyl, xylyl, ethylphenyl, butylphenyl, t-butylphenyl, dimethylnaphthyl or similar aryl groups; Benzyl, phenethyl, phenylpropyl or similar aralkyl groups; 3-chloropropyl, 3,3,3-trifluoropropyl or similar halogenated alkyl groups; Methoxyphenyl, ethoxyphenyl, butoxyphenyl, t-butoxyphenyl, methoxynaphthyl or similar alkoxy-substituted aryl groups. In the formula (4), f is an integer of 0 to 4.

The above-mentioned component (C) is available as a commercial product known under the trade name Epicoat 630 manufactured by Japan Epoxy Resin Company.

Although there is no particular limitation with respect to the amount of the component (C) that can be used in the composition, it is preferable to add the component in an amount of 0.01 to 50 mass%, preferably 0.01 to 20 mass%, and most preferably 0.01 to 10 mass% It can be recommended. If the content of component (C) is lower than the recommended lower limit, it will be difficult to limit oil-bleeding to the surface. On the other hand, if the content of component (C) exceeds the recommended upper limit, it will increase the modulus of the cured product obtained from the composition.

The composition of the present invention may contain a curing accelerator (D) as an optional component. Such component (D) is a tertiary amine compound; Alumina, zirconia or similar organometallic compounds; Phosphine or similar organic phosphorus compounds; As well as heterocyclic amine compounds, boron complexes, organic ammonium salts, organic sulfonium salts, organic peroxides, and reaction products of such compounds. Specific examples of such compounds include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine-triphenylborate, tetraphenylphosphine-tetraphenylborate Or similar phosphorus compounds; Triethylamine, benzyldimethylamine,? -Methylbenzyldimethylamine, 1,8-diazabicyclo [5,4,0] undecene-7 or similar tertiary amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole or similar imidazole compounds. To prolong the pot life of the compositions of the present invention, the cure accelerator may be in encapsulated form. Such an encapsulated curing accelerator may comprise an encapsulated amine based curing accelerator made from a bisphenol-A epoxy resin containing an amine based curing accelerator. The encapsulated curing accelerator can be purchased from Asahi Kasei Co., Ltd. under the trade name HX-3088.

The amount by which the component (D) can be added to the composition is not particularly limited, but it is generally not more than 50 parts by mass, particularly 0.01 to 50 parts by mass, and most preferably 0.1 to 5 parts by mass per 100 parts by mass of the component (A) It can be recommended that it is contained in a negative amount.

To improve the mechanical strength of the cured product, the composition may contain filler (E). Such component (E) may be selected from the group consisting of glass fibers, alumina fibers, ceramic fibers comprising alumina and silica, boron fibers, zirconia fibers, silicon carbide fibers, metal fibers or similar fibrous fillers; Silica glass, fused silica, fired silica, zinc oxide, fired clay, carbon black, glass beads, alumina, talc, calcium carbonate, clay, aluminum hydroxide, magnesium hydroxide, Boron, silicon carbide, magnesia, titania, beryllium oxide, kaolin, mica, zirconia, barium sulfate or similar inorganic fillers; Brass, solder, shape memory alloy powder or other metal powder: gold, silver, copper, aluminum, nickel, palladium and alloys of these metals, ceramic, glass, quartz or organic resin etc. Silver, nickel, or copper or other metal powder deposited on the surface of the substrate or deposited by plating. The fillers can be used individually or as a combination of two or more thereof. From the standpoint of good thermal conductivity of the resulting cured product, the following fillers are preferred: conductive powder such as alumina, crystalline silica, alumina nitride, boron nitride or similar thermally conductive powder; As well as reinforcing powder prepared from fused silica, precipitated silica, fumed silica, colloidal silica and the like. In order to impart excellent thermal conductivity and electrical conductivity to the cured product, it is preferable to use silver powder. In order to impart thermal conductivity to the cured product of the composition, it is preferable to use alumina powder. The powder particles may have a crushed particle form or may be spherical, fibrous, rod shaped, flaked, scaly, plate shaped, coiled, and the like. There are no particular limitations on particle size, but the maximum diameter thereof should generally not exceed 200 占 퐉, and the average particle size should be in the range of 0.001 to 50 占 퐉.

There is no particular restriction on the content of the component (E), but the amount of the component is not more than 5,000 parts by mass per 100 parts by mass of the component (A), preferably in the range of 10 to 4,000 parts by mass, It is recommended that the amount is 4,000 parts by mass. When component (E) contains a filler other than the above-mentioned metallic fine powder or thermally conductive powder material, component (E) is preferably used in an amount not exceeding 2,000 parts by weight per 100 parts by weight of component (A) Should be used in an amount in the range of 10 to 2,000 parts by mass, more preferably in the range of 50 to 1,000 parts by mass. When the powder particles are in the form of plates or scales, the shrinkage upon curing due to the use of the specific orientation of the particles in the resultant cured product can be reduced.

In order to improve the curability and workability of the composition and to improve the adhesion of the cured product of the composition or to control the modulus of elasticity, the composition may be further compounded with the organic epoxy compound (F). There are no particular restrictions on the form of component (F) at 25 DEG C, which may be liquid or solid, but liquid form is preferred. This component can be exemplified by bisphenol A type of epoxy resin, bisphenol F type of epoxy resin or alicyclic epoxy resin. There is no particular limitation on the amount of the component (F) added to the composition, but generally, the content of the composition should not exceed 500 parts by mass, preferably 0.1 to 500 parts by mass per 100 parts by mass of the component (A) .

To improve the dispersibility of component (E) in component (A) or to improve the adhesion of the resulting cured product to semiconductor chips, substrates, etc., the composition may be combined with a coupling agent. The coupling agent may be exemplified by a titanate coupling agent, a silane coupling agent or a similar coupling agent. The titanate coupling agent may comprise i-propoxytitanium tri (isostearate). Silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane or similar epoxy-containing alkoxysilane; N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane or similar amine-containing alkoxysilanes; 3-mercaptopropyltrimethoxysilane or similar mercapto-containing alkoxysilane; Octadecyltrimethoxysilane or similar long chain alkyl-containing silanes. The amount of the above-mentioned silane coupling agent is not particularly limited, but it is generally preferable to add the agent in an amount in an amount not exceeding 10 parts by mass, preferably in an amount of 0.01 to 10 parts by mass per 100 parts by mass of the component (A) Recommended.

Other optional components of the composition include tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyl Trimethoxysilane, trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, or similar alkoxysilane.

The composition of the present invention is prepared by mixing component (A), component (B) and component (C), if necessary, with other components. The method of mixing the components is not particularly limited. For example, the components (A), (B) and (C) and, if necessary, optional components are mixed at the same time, or the components (A), (B) Any of the ingredients listed may be added. There is also no particular limitation on the apparatus that can be used for mixing. For example, this first single shaft or two-shaft type continuous mixer, two roll mill, three-roll mill, Ross (Ross ^®) mixer, Hobart (Hobart) mixer, dental mixer, play four planetary mixer, a kneader mixer or a milling mixer days for .

In addition to being used as a protective agent for semiconductor chips or electrical wiring, the cured product of the composition of the present invention may be used in an insulating layer or buffer layer on a semiconductor chip or a printed circuit board. There are no particular restrictions as to the form of the cured product obtained from the composition, and the cured product may be prepared in the form of a rubber, a hard rubber or a resin, but most preferably the complex elastic modulus does not exceed 2 GPa.

The composition of the present invention is suitable for transfer molding, injection molding, potting, casting, powder coating, deposition coating, dropping coating, and the like. The method of use can be selected from potting, dispensing, screen printing, coating and the like, but from a viewpoint of facilitating the use of the material and reducing consumption, the composition is preferably in liquid or paste form. Since the composition of the present invention is suitable for forming a cured article characterized by excellent flexibility and adhesion, the composition can be used as an encapsulant, a casting agent, a coating agent, an adhesive, etc. for use with an electric device or an electronic device .

The following is a detailed description of the electronic component of the present invention. The electronic component of the present invention is characterized by the fact that it is sealed and adhered using a cured product of the composition of the present invention. Such components may include diodes, transistors, thyristors, monolithic ICs, hybrid ICs, LSIs, or VLSIs.

An example of an electronic component of the present invention is shown in Fig. 1 as a sectional view of an LSI. This figure illustrates an electronic component in which a heat-radiating material or an adhesive is formed using the curable silicone composition of the present invention. The electronic component shown in Fig. 1 includes a semiconductor element 1 which is provided on a substrate 2 having a circuit and is electrically connected to the substrate circuit through a solder bump such as a ball grid 3 provided on the semiconductor element 1, . The substrate may be made of glass reinforced epoxy resin, Bakelite resin, phenolic resin or similar organic resin; Alumina or similar ceramics; Copper, aluminum or similar metals. In addition to the semiconductor element 1, the electronic component may contain a resistor, a capacitor, a coil or other electronic component. Although the space between the semiconductor element 1 and the substrate 2 is shown filled with an underfiller material in Fig. 1, the use of such an underfiller material is arbitrary.

The semiconductor device 1 is connected to the heat spreader 4 through the heat dissipating member 6. The heat spreader 4 is bonded to the substrate 2 through the adhesive 5. Further, the heat spreader 4 is connected to the heat radiating plate 7 through the heat radiating member 8. The heat spreader 4 and the heat sink 7 may be made of aluminum, copper, nickel or similar metals. In the electronic device shown in Fig. 1, the adhesive 5 is made of a cured product of the curable silicone composition of the present invention. Further, in the electronic component of Fig. 1, the heat radiating member 6 and / or the heat radiating member 8 may also be made of a cured product of the curable silicone composition of the present invention. The cured product of the curable silicone composition of the present invention can be used to adhere the semiconductor element 1 to the heat spreader 4 or adhere the heat spreader 4 to the substrate 2. [ For the convenience of maintenance, the heat dissipating member 8 can be replaced with a thermal conductive grease.

The method for producing the electronic component of the present invention is not particularly limited. For example, the structure shown in Fig. 1 can be manufactured as follows. First, the semiconductor element 1 is placed on the substrate 2, and the semiconductor device 1 is electrically connected to the substrate 2 by using the ball grid 3. Then, if necessary, underfiller material is used. In the next step, the surface of the semiconductor element 1 is coated with a curable silicone composition having thermal conductivity, the heat spreader 4 is attached, and the curable silicone composition is cured. Thereby, the heat spreader 4 is bonded to the substrate 2 through the cured silicone composition coated on the heat spreader. In the next step, a curable silicone composition having a heat conductive property or a thermal conductive grease is applied onto the heat spreader 4 and the heat sink 7 is attached. When the heat spreader is coated with a curable silicone composition, the latter is cured.

The curable silicone composition and electronic components of the present invention will be described in more detail with reference to Examples and Comparative Examples. All viscosity values used in the Examples correspond to the viscosity values at 25 占 폚. The mass average molecular weight was determined by gel permeation chromatography using toluene as a solvent and calculated by using polystyrene as a standard.

[Viscosity]

This property was measured using an E-type viscometer DV-U-E II-Type (manufactured by Tokimec Company, Ltd.) at 25 ° C at a rotation speed of 2.5 rpm.

[Adhesiveness]

A specimen was prepared by adhering a 50 탆 thick layer of a curable silicone composition on an alumina panel to a silicon chip having a square cross section of 10 mm x 10 mm and then heating at 150 캜 for 1 hour to cure the curable silicone composition described above. The obtained specimens were tested for peel strength (kgf / cm ² ) at 25 ° C and 50 mm / min in a bond tester (Model SS-100KP, Seishin Trading Company, Ltd.).

[Complex modulus of elasticity]

After removing the air, the curable silicone composition was filled in a mold cavity having a width of 10 mm, a length of 50 mm and a depth of 2 mm, press curing at 150 DEG C for 60 minutes under a pressure of 2.5 MPa, To obtain a specimen of the cured product of the composition. The complex modulus of the specimen was measured using an ARES viscoelastic analyzer from Rheometric Scientific, Inc. Measurements were made at 25 DEG C with a strain of 0.05% and a frequency of 1 Hz.

[Oil-Bleeding Property]

0.2 g of the curable silicone composition was dropped on the surface of the ground-glass plate and left at 25 캜 for 48 hours. The oil-bleeding property was evaluated by the following formula.

10O x (L ₁ - L ₀ ) / L ₀

In the above equation,

L ₀ is the diameter of the curable silicone rubber,

L ₁ is the diameter formed by oil-bleeding.

[Example 1]

4.38 parts by weight of an organopolysiloxane having the following average unit formula:

(Mass average molecular weight = 1,000; viscosity = 1,290 mPa 占 퐏; epoxy equivalent = 267);

8.46 parts by mass of organotrisiloxane of the following formula

(Viscosity = 2,600 mPa · s; phenolic hydroxyl group equivalent = 330);

0.99 parts by mass of an epoxy compound of the following formula:

0.43 parts by mass of octadecyltrimethoxysilane; 68.64 parts by mass of spherical alumina particles having an average particle size of 8.6 占 퐉; 15.92 parts by mass of irregularly shaped alumina particles having an average particle size of 3 占 퐉; And 1.19 parts by mass of a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin containing 35 mass% of an encapsulated amine-based catalyst (HX-3941HP, product of Asahi Kasei Corporation) were mixed to prepare a curable silicone composition. The properties of the curable silicone composition and its cured product are shown in Table 1.

[Comparative Example 1]

6.43 parts by weight of an organopolysiloxane having the following average unit formula:

(Mass average molecular weight = 1,000; viscosity = 1,290 mPa 占 퐏; epoxy equivalent = 267);

7.57 parts by mass of organotrisiloxane of the following formula

(Viscosity = 2,600 mPa · s; phenolic hydroxyl group equivalent = 330); 0.43 parts by mass of octadecyltrimethoxysilane; 68.54 parts by mass of spherical alumina particles having an average particle size of 8.6 占 퐉; 15.89 parts by mass of irregularly shaped alumina particles having an average particle size of 3 占 퐉; And 1.14 parts by mass of a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin containing 35% by mass of an encapsulated amine-based catalyst (HX-3941HP, product of Asahi Kasei Corporation) were mixed to prepare a curable silicone composition. The properties of the curable silicone composition and its cured product are shown in Table 1.

[Example 2]

8.0 parts by weight of an organopolysiloxane having the following average unit formula:

(Mass average molecular weight = 1,000; viscosity = 1,290 mPa 占 퐏; epoxy equivalent = 267);

10.7 parts by mass of organotrisiloxane of the following formula

(Viscosity = 2,600 mPa · s; phenolic hydroxyl group equivalent = 330);

0.5 parts by mass of an epoxy compound of the following formula

62.9 parts by mass of spherical alumina particles having an average particle size of 8.6 占 퐉; 17.1 parts by mass of irregularly shaped alumina particles having an average particle size of 3 占 퐉; And 0.8 mass part of a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin containing 35 mass% of an encapsulated amine-based catalyst (HX-3941HP, product of Asahi Kasei Corporation) were mixed to prepare a curable silicone composition. The properties of the curable silicone composition and its cured product are shown in Table 1.

[Comparative Example 2]

7.7 parts by weight of an organopolysiloxane having the following average unit formula:

(Mass average molecular weight = 1,000; viscosity = 1,290 mPa 占 퐏; epoxy equivalent = 267);

10.7 parts by mass of organotrisiloxane of the following formula

(Viscosity = 2,600 mPa · s; phenolic hydroxyl group equivalent = 330);

1.5 parts by weight of organotrisiloxane of the following formula

(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₂₅ Si (CH ₃ ) ₂ -Z

(Wherein Z is a group represented by the formula

의 디메틸폴리실록산이다)(질량 평균 분자량 = 2,500; 점도 = 75mPa·s); 평균 입자 크기가 8.6㎛인 구형 알루미나 입자 62.9질량부; 평균 입자 크기가 3㎛인 불규칙한 형태의 알루미나 입자 17.1질량부; 및 캡슐화된 아민계 촉매(HX-3941HP, 아사히 가세이 캄파니 리미티드 제품) 35질량%를 함유하는 비스페놀 A형 에폭시 수지 및 비스페놀 F형 에폭시 수지의 혼합물 0.8질량부를 혼합하여 경화성 실리콘 조성물을 제조하였다. 경화성 실리콘 조성물 및 이의 경화물의 특성을 표 1에 기재한다.

(Mass average molecular weight = 2,500; viscosity = 75 mPa 占 퐏); 62.9 parts by mass of spherical alumina particles having an average particle size of 8.6 占 퐉; 17.1 parts by mass of irregularly shaped alumina particles having an average particle size of 3 占 퐉; And 0.8 mass part of a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin containing 35 mass% of an encapsulated amine-based catalyst (HX-3941HP, product of Asahi Kasei Corporation) were mixed to prepare a curable silicone composition. The properties of the curable silicone composition and its cured product are shown in Table 1.

[Example 3]

6.2 parts by weight of an organopolysiloxane having the following average unit formula:

(Mass average molecular weight = 1,000; viscosity = 1,290 mPa 占 퐏; epoxy equivalent = 267);

10.5 parts by mass of organotrisiloxane of the following formula

(Viscosity = 2,600 mPa · s; phenolic hydroxyl group equivalent = 330);

2.0 parts by mass of an epoxy compound of the following formula

(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₂₅ Si (CH ₃ ) ₂ -Z

(Wherein Z is a group represented by the formula

의 디메틸폴리실록산이다)(질량 평균 분자량 = 2,500; 점도 = 75mPa·s);

(Mass average molecular weight = 2,500; viscosity = 75 mPa 占 퐏);

The

의 에폭시 화합물 0.5 질량부;

0.5 parts by mass of an epoxy compound;

62.9 parts by mass of spherical alumina particles having an average particle size of 8.6 占 퐉; 17.1 parts by mass of irregularly shaped alumina particles having an average particle size of 3 占 퐉; And 0.8 mass part of a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin containing 35 mass% of an encapsulated amine-based catalyst (HX-3941HP, product of Asahi Kasei Corporation) were mixed to prepare a curable silicone composition. The properties of the curable silicone composition and its cured product are shown in Table 1.

[Example 4]

3.3 parts by mass of dimethylpolysiloxane having the following average unit formula:

X-CH ₂ CH ₂ (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] ₁₆₂ Si (CH ₃ ) ₂ CH ₂ CH ₂ -X
Wherein X is an organopolysiloxane residue radical of the following average unit formula:

delete

_{[Y (CH 3) 2 SiO} 1/2] 1.6 (SiO 4/2) 1.0
Wherein Y is a single bond, a trimethoxysilylpropyl group and a 3-glycidoxypropyl group, at least one Y in one molecule is a single bond and the other Y is used in a molar ratio of 1: 4 Trimethoxysilylpropyl and 3-glycidoxypropyl groups)} (mass average molecular weight = 51,000; viscosity = 12,000 mPa 占 퐏);

delete

6.0 parts by weight of an organopolysiloxane having the following average unit formula:

(Mass average molecular weight = 1,000; viscosity = 1,290 mPa 占 퐏; epoxy equivalent = 267);

9.4 parts by mass of the following organotin siloxane

(Viscosity = 2,600 mPa · s; phenolic hydroxyl group equivalent = 330);

0.5 parts by mass of an epoxy compound of the following formula

(Viscosity = 2,600 mPa · s; phenolic hydroxyl group equivalent = 330);

62.9 parts by mass of spherical alumina particles having an average particle size of 8.6 占 퐉; 17.1 parts by mass of irregularly shaped alumina particles having an average particle size of 3 占 퐉; And 0.8 mass part of a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin containing 35 mass% of an encapsulated amine-based catalyst (HX-3941HP, product of Asahi Kasei Corporation) were mixed to prepare a curable silicone composition. The properties of the curable silicone composition and its cured product are shown in Table 1.

Example

characteristic                  Example      Comparative Example      One     2     3      4      One      2 Viscosity
(Pa.s)    226     42     73    100    159    120 Adhesiveness
(kgf / cm ² )     80   > 100     95     87     53     68 Oil-bleeding property     0.5    0.5     12     8     18     20 Complex modulus
(MPa)     510    1800    250   400    330    111

Since the curable silicone composition of the present invention is characterized by excellent handling workability, it is suitable for transfer molding, injection molding, potting, casting, powder coating, deposition coating, dropping coating and the like. Further, after curing, the composition forms a cured product characterized by excellent flexibility and adhesiveness, so that the composition is suitable for use as a sealant, a casting agent, a coating agent, an adhesive, etc. for parts of electric and electronic devices Do. In particular, when the composition contains a thermally conductive filler, the composition can be used as a heat dissipating member and a heat dissipation interface material (TIM).

Claims (15)

(A) an organopolysiloxane (A ₁ ) represented by the average unit formula of the formula ( ₁ ) and / or a diorganopolysiloxane (A ₂ ) represented by the formula (2) containing two or more epoxy-containing monovalent organic groups in one molecule, (B) a curing agent for an epoxy resin and (C) an epoxy compound of the formula (4). Formula 1 (R ¹ ₃ SiO _1/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ³ SiO _3/2 ) _c In the above formula (1) R ¹ , R ² and R ³ may be the same or different and represent a substituted or unsubstituted monovalent hydrocarbon group or an epoxy-containing monovalent hydrocarbon group, but at least 20 mole% of the group represented by R ³ is an aryl group , a, b, and c satisfy the conditions of 0? a? 0.8, 0? b? 0.8, 0.2? c? 0.9, and a + b + c = (2) AR ⁵ - (R ⁴ ₂ SiO) _m R ⁴ ₂ Si-R ⁵ -A In the above formula (2) R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having no unsaturated aliphatic bond, R &lt; ⁵ &gt; is a divalent organic group, A is a siloxane residue radical represented by the average unit formula of the formula (3) m is an integer of 1 or more. (3) (XR ⁴ ₂ SiO _1/2 ) _d (SiO _4/2 ) _e In the above formula (3) R ⁴ is the same as defined above, X is a single bond, a hydrogen atom, a group represented by R ⁴ , an epoxy-containing monovalent organic group or an alkoxysilylalkyl group, but at least one group represented by X in one molecule is a single bond and two or more Group is an epoxy-containing monovalent organic group, d is a positive number, e is a positive number, d / e is a number in the range of 0.2 to 4. Formula 4

In the above formula (4) R ⁸ is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 10 carbon atoms, f is an integer of 0 to 4; The curable silicone composition of claim 1, wherein said component (B) is a compound having a phenolic hydroxyl group. The curable silicone composition according to claim 2, wherein the component (B) is an organosiloxane containing two or more phenolic hydroxyl groups in one molecule. The curable silicone composition of claim 3, wherein said component (B) is an organosiloxane of formula (5). Formula 5 R ⁶ ₃ Si0 (R ⁶ ₂ SiO) _n SiR ⁶ ₃ In the above formula (5) R &lt; ⁶ &gt; is a monovalent organic group containing a substituted or unsubstituted monovalent hydrocarbon group or a phenolic hydroxyl group, but a monovalent organic group in which at least two R &lt; ⁶ &gt; groups in one molecule contain a phenolic hydroxyl group ego, and n is an integer ranging from 0 to 1000. The curable silicone composition according to claim 1, wherein the component (B) is contained in an amount of 0.1 to 500 parts by mass per 100 parts by mass of the component (A). The curable silicone composition according to claim 1, wherein the component (C) is contained in an amount of 0.01 to 50 mass% of the curable silicone composition. The curable silicone composition according to claim 1, further comprising a curing accelerator (D). 8. The curable silicone composition of claim 7, wherein said component (D) is an encapsulated amine-based cure accelerator. The curable silicone composition according to claim 7, wherein said component (D) is contained in an amount not exceeding 50 parts by mass per 100 parts by mass of component (A). The curable silicone composition of claim 1, further comprising a filler (E). The curable silicone composition according to claim 10, wherein said component (E) is contained in an amount not exceeding 5,000 parts by mass per 100 parts by mass of component (A). 11. The curable silicone composition of claim 10, wherein said component (E) is a thermally conductive filler. The curable silicone composition according to claim 1, further comprising an organic epoxy resin (F). The curable silicone composition according to claim 13, wherein said component (F) is contained in an amount not exceeding 500 parts by weight per 100 parts by weight of component (A). An electronic component which is sealed or bonded by a cured product of a curable silicone composition according to any one of claims 1 to 14.

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